DE3305373A1 - ELASTIC MATERIAL, METHOD FOR PRODUCING AND MOLDING AND USE THEREOF - Google Patents

Description

Elastic molding compound, method of manufacturing and deforming and use of the same

The invention relates to elastic molding compositions based on thermoplastic rubber, which as Filler contain at least one silicate filler.

Thermoplastic rubber in the context of the present invention is a thermoplastic, the Understood polymer exhibiting elastic behavior analogous to conventional rubber, which is based on known manner is produced from the monomers styrene and butadiene or styrene and isoprene or Ethylene and propylene. The thermoplastic rubbers are block copolymers, e.g. three-block copolymers, which consist of two phases. These copolymerized Elastomers do not need to be vulcanized. So that these copolymers have the desired good elasticity - Show behavior, your entire polystyrene content will

kept below about ko $. 30th

The thermoplastic rubbers described (abbreviated to TR) are also referred to as teleblock rubbers.

35- ■ '

The use of highly disperse silica fillers, such as those from aqueous solutions, is also known

made of water glass by precipitation with acid finely divided fillers consisting essentially of silica in thermoplastic rubber. The addition of silica improves the appearance of thermoplastic shoe soles, for example Plastic, in which the soles get a desired fashionable matting effect, further increased The addition of silica reduces the friction in the production of the mixtures, which means that © ine improves the raid

IQ faster distribution of all components of the mixture is achieved. Furthermore, the absorption of the processing oil that is advantageously also used is improved by the thermoplastic rubber, for example. accelerated, thereby reducing the mixing times. The it iron ζ bondability, too. The soles of the shoes are improved and the separation strength increased. Other advantages of the co-use -from silica fillers can for example increase the tensile strength of the voltage value and the Shore hardness of the manufactured

20 put to be molded body.

However, these advantages are offset by two disadvantages. The use of silica as a filler Firstly, it leads to an increase in viscosity that is dependent on the degree of filling, which is due to operational malfunctions

cause overloading of processing machines and, secondly, to increased absorption of elasticity of the manufactured goods, since the silica fillers produced by precipitation are nygros- ^ O are copical and depending on the relative Humidity absorb moisture

The rubber compound is already taking n & uh. Incorporation of this filler into the thermoplastic rubber absorbs moisture or water, which is why this is not active

is prevented. Consumer goods, which are based on a mixture containing silica filler are made of thermoplastic rubber, Depending on the ambient conditions, considerable amounts can be used

5 absorb moisture and are thereby greatly reduced in their utility value.

It has now been found that the disadvantages described, such as increased viscosity and moisture absorption can be mitigated, and that because of the improvement in physical properties the Use of larger amounts of filler in thermoplastic rubber is made possible.

The invention relates to an elastic molding compound containing or consisting of a (m) thermoplastic rubber or a (em) mixture of such rubbers, optionally in a mixture with a thermoplastic and / or a

^ O synthetic resin further comprises at least one (m) silicate filler in quantities of 1 to 300 parts by weight preferably 1 to 150 parts by weight, processing ^ - or plasticizer oil in amounts of 0 to 100 parts by weight, and at least one (em) Stability ° lisierungsmittel from the group of aging, fatigue, oxidation, ozone and light protection agents in customary amounts, which is characterized in that it contains at least one organosilicon compound which has at least one alkoxysilyl group, in amounts of 0.1 to 25 parts by weight, preferably 0 , 1 - 15 parts by weight, all parts by weight being based on 100 parts by weight of thermoplastic rubber, or that the molding compound contains the organosilicon compound mentioned or the

called organosilicon compounds in a mixture

with the silicate filler, or that the molding compound contains the said organosilicon compound or the organosilicon compounds mentioned in a form chemically bonded to the silicate filler

5 contains in an even distribution.

The invention also relates to an elastic molding compound which is characterized in that it contains at least one organosilane of the formulas as organosilicon compounds

IX -CH " _i -SiR ¹ (OR)", ρ m 2m + 1-pn ^{v 7} 3-n '

in which X is chlorine or bromine, ρ = 1 or 2, m = 1 to 5 »R is a C ₁ - to C" -alkyl group, a 0 _ς - to C, - cycloalkyl group or the phenyl group, R is a C ₁ - to C "-alkyl group, a C_- to C, - Cyc Io alkyl group, the methoxyethyl group, the ethoxyethyl group, phenyl group or the benzyl group and η = O j 1 or 2, including a hydrolyzate and / or a condensate,

fr:

II IR _n (RO) _{> n} Si- (Alk) _q (Ar) _r -J ₂ S _x or

25 ι (ro)

III R _n ^v 'Si-AIk-SH,

in which Ar is an arylene radical with 6 to 12 carbon atoms r = 0 or 1, R a C ₁ - to C "-alkyl group, the phenyl group, R a C ₁ - to C" -alkyl group, the

Of) - ^

Methoxyethyl group, ethoxyethyl group, phenyl group or benzyl group, η = 0 | II or 2, Alk is a divalent, straight or branched hydrocarbon radical with 1 to 6 carbon atoms, and π is a number voa 2.0

up to 8.0, preferably up to 6.0 including theirs

Hydrolysates and / or their condensate qsO or 1 and, as silicate fillers, at least one filler _{t of} the ± m essentials obtained by filling from an aqueous medium

consists of silica with specific surface areas, measured according to DIN 66 132, between 30 and 250 m / g, or the molding compound contains a mixture of or a chemical reaction product of at least one of said organosilanes and at least one of said silica fillers or carbon black instead of Individual components of the mixture or the reaction product or instead of part of these individual components.

10 To the Haiögenalkylalkoxy- and phenoxysilanes of Formula I count in particular

Chloromethyl trimethoxysilane, chloromethyltria-fchoxysilane, Brommethyitriäthoxysilan, Dichlomethyltriätlioxysilan,

1-chloro-1-met! Hyl-inethyl-triTnethox3 ^r silane, 2-Clilor Ib

■ äthyltrimethoxysilan, 2-Broinäthyltrimethoxyjsllan, 2-dibromoethyltrimethoxysilane, 3-bromopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-dichl.orpropyltrimethoxysilane, 3-chloropropyltrethoxysilane, 3 - bromine

20 "

propyltriäthoxysilan, 3-Dibrompropyltriäthoxysilan, 2-bromo-1-methyl-äthyltripropoxysilan, 2-DichloräthyA- tri-n-butoxysilane, 2-tri- Qiloräthyl-2 ^{r-methyl-propoxysilane,} 3-bromopropyl-tri-t-butoxysilane _f 3 -DIbromopropyltriisopropoxysilane, 3-bromopropyltr -n-pentoxysilane, 2-chloroethyl-tri- ^2f -ethyl-ethoxy-la3i, 2-bromo-2-methyl-ethyldimethoxyethoxysilaii, 3-dichloropropyl-methoxyethoxypropoxysilane , 3-CjtI.loΓpΓopyldi! 3 ^ e ■ tllO3cy—

10 methylsilane, 3-B ^rom P ^ro Pyldiäthoxyäth.yls ± lan,

3-chloropropylethoxydiethylsilane, 3-bromopropyl- tris- (1 '-methoxyethoxy) - silane, 3-chloropropyldlätlioxyphenylsilan, 3-dichloropropyldimethozycyclopentylsilane, 3-bromopropyl-di-n-propoxy-cycloliexylsilaii, 3-chloro-

15 propyldicycloliexoxypyclohexyleilaja, -

3-Ciilorpropylä-fchoxyph.eiiyl-

oxyethylsilane, 3-dibromopropylbeIlzyloΣyätllO23rathyl5ilaIl, 4-chloro-n-butyltrimeth.oxysilane, 4-bromobu-fcyi-fcrimetlioxysilane, 3-chloro-2-methyl-propyltrimetlioxysilaai,

_w ·, 3-CM.or-.2-

ethyl-propyldiäthoxymetliylsilaii, 3-BrOm-S-StIIyI-propyldimethoxymethylsilan, 3-chloro-2-me1; hyl — propyl— dimethoxyphenylsllane, 5-chloro-n-pentyltriätboxysilane,

2-methyl-butyltriäthoxysilan, 2-ClllOΓ-2-metIlyl-äthyltripentoxyaileai, 2-dichloΓ-2-methyl-ethyltΓibutylo2ysilane, 3-Bromopropyltriphenoxysilaii, 3-Clilorpropyltx * ibe2izyl— oxysiian, 3-dibromopropyltricyclopentoxysilane and 3-bromine propyltri-n-pentoxysilane. The haloalkyloxysilanes are being pulled with one halogen atom (p = 1 in formula I) and with three alkoxysilyl groups.

- 1 1 -

The oligosulfidic silanes of the formula II, which are known per se, for example from US-PS

3 873 489, and those made according to the procedures set out in the DE-PS 25 42 534 and DE-AS 25 58 191 are described, can be prepared, count in particular the bis (trialkoxyeilyl-alkyl) -oligosulfide. Of these Trialkoxysilanes and their mixtures of the general Formula II are again preferred to the bis (3-trimethoxy-, - (3-triethoxy- and - (3-tripropoxysilyl-propyl) -polysulfides) namely the di-, tri- and tetrasulfides, especially the triethoxy compounds with 2, 3 or

4 sulfur atoms and their mixtures. These oligosulfidic silanes are preferably used in amounts of 1 to 15 parts by weight per 100 parts by weight of silicate filler in the new thermoplastic Rubber mixtures used / to be used advantageously are above all

3 ^

(C ₂ H ₅ O) ₃ Si (CH ₉ )

2 '2

Λ / 3

and

(C ₂ H ₅ O) ₃ Si (CH ₉ )

2'2

and methoxy analogs

- 12 -

The following mercaptosilanes of the formula III are preferably used:

Mercaptomethyltrimethoxysilane, mercaptomethyltri- ethoxysilane, mercaptomethyltri-i-propoxylsilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltri-i-propoxysilane, 2-Mercaptoäthyltributoxysilaii, 2-Mercaptoätiiyltrin-propoxysilan, 2-mercaptoethyl diethoxycethylsilane,

2-mercapto-2-methylethyl-diethyl oxysil, 2-mercapto 15th

1-methylethyl-trimethoxysilane, 3-mercaptopropyltri-

methoxysilane, 3 ~ mercaptopropyltriättioxysilaii,

3 mercaptopropyltri-i-propoxysilane, 3 ~ mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltributoxysilane,

3-mercaptopropyltris- (metnoxyätIioxy) -s ± lan _f 4-mer-

captobutyltriethoxysilane, 5-mercaptopentyltrimethoxysilane, 5-mercaptopentyltri-i-propoxysilane, 3-mercaptopropyl diethoxyethylsilane, 3-mercaptopropyldipropoxypropylsilane, e-mercaptohexyltriethoxysilane.

Instead of the listed organosilicon compounds, in particular those of the formulas I, II and III, their hydrolysates and condensates can also occur, possibly partially, which means mixtures of the non-hydrolyzed or non-condensed silanes with the hydrolyzed and / or condensed silanes are meant. This hydrolysis or co.ndensation is necessary not to be complete, so that partial hydrolysates or partial condensates can also be used according to the invention can come. These partial hydrolyzates or partial condensates can be produced when the silanes have several oxysilyl groups in the molecule.

The condensates include in particular the condensates the silanes with alcohols, preferably dihydric alcohols such as ethylene glycol, propylene glycol, Trimethylene glycol, trimethylethylene glycol, tetramethylene glycol, Pentamethylene glycol etc, diethylene glycol, Butanediols such as 1,4-butanediol, dipropylene glycol, polyethylene glycols and glycid (2,3-epoxypropanol-i)

The hydrolysis as well as the condensation reactions are carried out according to methods known per se. she lead to higher molecular compounds with e.g. higher boiling points etc., which is important for the production of the molding compositions according to the invention can be advantageous.

According to the invention can be used individually or in a mixture

furthermore organosilanes of the formula 30th

IV A-SiR ¹ (OR)

3-n

in which n, R and R have the meanings given above and A is an azido or thiocyanato, amino or

35— ■■ - - - - ■ - ■ - ■ · - ■

Epoxyalkyl group with a straight or branched one Cj-Cg hydrocarbon radical as alkyl, or a vinyl group or is an aralkyl radical.

Thiocyanatoalkylalkoxysilanes are particularly suitable like 3-Thiocyanatopropyltrimethoxy-, -triäthoxy-, -tri-n-propoxy-. -tri-isopropoxysilane and the corresponding 2-Thiocyanatoäthylalkoxysilane, also Vinylalkoxysilanes such as

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripopoxysilane, Vinyl-tris-i-propoxysilane, vinyl-tris- (2-methoxyethoxy) -silane, Divinyl diethoxysilane, divinyldimethoxysilane, divinyl-di-i-propoxysilane, divinyl-di-npropoxysilane, Vinylmethyldimethoxysilane, vinylethyldiethoxysilane, vinylmethyl-di- (2ethoxy-ethoxy) -silane, Vinyl diethylethoxysilane, vinyldimethylmethoxysilane, ' Vinyl diethyl-2-methoxyethoxy-silane, vinylphenyldiethoxysilane, Vinyldiphenylmethoxysilane, being monovinylsilanes are preferred.

Of the azidosilanes, azidomethyltriethoxysilane, 2-azidoethyltriethoxysilane, 3-azidopropyl-

triethoxysilane and the corresponding methoxy analogs

used.

Silanized polybutadienes are also very suitable. These include polybutadienes of different molecular weights and vinyl group content to understand the 25th

Double bonds have been at least partially saturated by reaction with reactive organosilanes.

The thermoplastics used according to the invention

_In particular, types of rubber include block copolymers

of the structure polystyrene-polybutadiene, polyisoprene-polystyrene, especially triblock copolymers, however also copolymers based on ethylene propylene.

- 13 -

The mandatory to be used according to the invention Fillers, including mixtures of two or more fillers, are inherent in rubber technology known fillers. The term "is more silicate Filler "a broad one and refers to fillers made up of silicates, silicates contain and / or contain chemically bound silicates in the broadest sense.

The claimed group of silicate fillers, which are essential to the invention, have silanol groups on the particle surfaces that are able to chemically react with the alkoxysilyl groups and similar oxy groups such as the phenoxy group of the organosilicon compounds to form -Si-O-Si bridges . In particular, the silicate fillers include »

Highly dispersed silica fillers, essentially consisting of silicon dioxide, with specific surface areas in the range from about 5 to 1000, preferably 20 to 400 m / g (according to the nitrogen adsorption method, which is described in the German industrial standard DIN 66 132, measured) and with primary particle sizes in the range of about 10 to 400 nm, which can be produced, for example, by precipitation in an aqueous medium, through hydrothermal digestion, by hydrolytic and / or oxidative high temperature conversion, also called flame hydrolysis, ^ O of volatile silicon halides (fumed silica) or by an arc process. These silica-containing fillers can optionally also be used as Mixed oxide or oxide mixture with the oxides of the metals aluminum, magnesium, calcium, barium, zinc and / or titanium are present.

Synthetic silicates, e.g. aluminum silicates or alkaline earth silicates such as magnesium or calcium silicate, with specific surface areas of about 20 to 400 m / g and primary particle sizes of about 10 to 400 nm.

Natural silicates, e.g. kaolins, clays, pebble circles 10 and asbestos as well as natural silicas such as Quartz e.g. as finely powdered quartz sand and kieselguhr (diatomaceous earth).

Glass fibers and glass fiber products such as mats, strands, fabrics, scrims and the like, as well as micro-glaze balls.

The silicate fillers mentioned are preferably used in amounts of 1 to 300 parts by weight Quantities from about 5 to

20 to about 150 parts by weight based on 100 parts by weight of the thermoplastic rubber.

The following filler mixtures can be named * Silica fillers of various origins, 25 silica / kaolin or silica / glass fibers / asbestos as well as blends of the silicate-containing reinforcing fillers with the well-known rubber blacks such as silica / HAF carbon black or silica / fiberglass cord / ISF carbon black.

Typical examples of those that can be used in the present invention Silicatic fillers are e.g. those manufactured and sold by DEGUSSA Aktiengesellschaft Silicas or silicates with the trade names AEROSIL ^, ULTRASIL ** ", SILTEG ^, DUROSIL ^, EXTRUSIL CALSIL ®.

330537

According to the invention, as silicate fillers the above-mentioned highly disperse or active silica fillers are preferred, in particular the precipitated ones Silicas, preferably in amounts from 5 to 150 parts by weight based on 100 parts by weight thermoplastic rubber.

An advantageous variant consists in using the organosilicon compound (s) with the (m) silicate filler (s) to react at elevated temperature, presumably the silanol groups of the silicate filler with the (n) oxysilyl group (s) react. These silanized silicate fillers can then be mixed with the remaining mixture constituents.

15 parts can be processed into the molding compound.

According to another variant with advantages, the organosilicon compounds are normalized Temperature mixed with the (n) silicate fillers and the resulting premix for production the molding compounds used. The above-mentioned premix can be prepared using intensively acting powder mixers be made in this way, for example according to DE PS 27 47 277

25 that a storable, non-dusty one

Premix, which can be incorporated particularly well and evenly into the rubber mixture, is created. When using this premix it can be advantageous to add the necessary amount of organosilicon compound (s) do not mix with all the necessary amount of filler in advance, but only with one Proportion of the necessary filler. So are beneficial such premixes enriched with respect to the organosilicon compound (s) can be used as in the case of

for example by weight according to 50 * 50 mixtures of Organosilicon compound (s) and filler (s).

I desired, such as for the purpose of coloring, can in fiction, according to s molding compound also. Soot be present. It can generally be added in amounts between 0.1 to 50 parts by weight per 100 parts by weight of rubber, 5 optionally in small amounts

Mixture to be incorporated. All types of soot come here, especially those used in the rubber industry commonly used types of carbon black in question. For example, HAF carbon blacks and especially ISAF carbon blacks are ge-10 called. If carbon black or carbon blacks are also used in the molding compound, the amount of silica fillers be lowered.

The plasticizer oil which can also be used according to the invention is an optional component of the new molding compound with a proportion of the plasticizer oil in the molding compound in Limits from about 0 to about 100 parts by weight per 100 parts by weight rubber, preferably within limits between 5 and 80 parts by weight per 100 parts by weight Rubber.

Plasticizer oils, which are also referred to as processing oils, are preferably of the naphthenic type Oils used. Plasticizer oils with a pour point between 0 and - 60 C are particularly advantageous, 25 preferably between - 10 and - 55 C. However, plasticizer oils of a highly aromatic nature can also be used Use.

The stabilization "0", which may also be used lizing agents, selected from the group of aging, fatigue, oxidation, ozone and light protection agents, are well-known substances in the rubber processing industry and they are used in common Quantities, i.e. in quantities of 0.1 to 10 parts by weight per 100 parts by weight of thermoplastic rubber, used.

330537

Optionally, the molding compositions can be further in additives known to the rubber processing industry can be added in customary amounts, such as e.g. pigments, dyes, waxes, other fillers such as chalk, aluminum oxides and known agents for Adhesion improvement between filler or inserts such as e.g. steel cord and the rubber matrix.

The lower for some components of the molding compounds

XO quantity limit indicated number zero means in the frame of the present invention that this component does not have to be present in the molding composition, but can. If this constituent, such as plasticizer oil, is present in the molding compound, the lower quantity limit is in practice at about 0.5 parts by weight, possibly even less, again based on 100 parts by weight rubber.

The molding compositions are produced in the usual way and in known mixing devices. Preferably is mixed in two separate stages. In the first stage, e.g. in a fast running Internal mixer in a time of 2 to 30 minutes with a speed of 20 to 120 per minute and an initial temperature of 90 to 110 ° C, the thermoplastic rubber with the silicate Filler (in one or more identical positions one after the other) and the organosilane mixed and, in the second stage the resulting mass on mixing rollers at an initial temperature (the rollers) of

90 to 110 ° C processed into a uniform rolled sheet within a time of 1 to 10 minutes, wherein the mill skin is cut or tipped three to five times with a knife. In the end If necessary after cooling, the rolled sheet with a thickness of 2 to 20 mm of the mixing roller device taken. If necessary, the rolled head

- 20 -

comminuted to granules or the like customary shaped pieces, and these are at temperatures between 6o and 300 ° C processed into moldings with the help of conventional devices.

The molding compositions according to the invention are used to produce shoe soles, sole plates or other molded bodies their shaping by injecting the molding compound into a metal or plastic mold or by Passing the molding compound through a shaping nozzle, as in the case of profiles, hoses, tapes or Threads are made »used.

33053 ¹ /

- 21 1 examples

The following examples are intended to illustrate the invention, but not to restrict it to the examples.

5 Example group A

In a basic mixture of 100 parts by weight of a thermoplastic rubber based on a styrene-butadiene-styrene block copolymer (Cariflex ^ TR-4i13 from Shell) and 50 parts by weight of a silica filler produced by precipitation with a specific surface (DIN 66132) of 175 m ² / g and an average primary particle size of 18 micrometers (Ultrasil ^ VN 3 from Degussa AG), various organosilicon compounds were incorporated in the specified amount.

a) 7.5 parts by weight of bis (3-triäthoxysilylpropyltetrasulfan

b) 6.6 parts by weight of bis (3-triäthoxysilylpropyl) -2Q disulfan

c) 6.2 parts by weight of 3-thiocyanatopropyltrimethoxysilane

d) 7.8 parts by weight of vinyl tris (2-methoxyethoxy) -s 11

e) 6.7 parts by weight of 3-chloropropyltriethoxysilane

f) 5 »5 parts by weight of 3-mercaptopropyltrimethoxysilane g) 7.5 parts by weight of phenylethyl diethoxysilane h) 7» 5 parts by weight of silanized polybutadiene oil see leaflet Polyvest 3324 "Polymeric Si filler activator for rubber ^{mixtures 1} (Polyveet 25 from Chem. Werke Hüls in Mari) l) 6.9 parts by weight of 3-azidopropyltriethoxysilane j) 7-35 parts by weight of thiocyanatopropyltriethoxysilane

Moldings 0.3 χ 1.7 cm in size, designed as rectangular profiles, were produced in any length by means of an extruder from the respective mixtures.

_ 22 -

1 In the same way, comparison files from the Basic mixture produced that contained filler and no organosilane (V2). On the filler-free Basic mixture (V1), could this

driving style do not apply. In order to achieve smooth surfaces, the thermoplastic rubber had to be shaped in a press using a metal mold to form a plate with 2 plane-parallel surfaces.
10

The following properties were tested or measured on the samples (moldings):

1. The tensile strength (ZF) in MPa according to DIN (53504) 2. The stress value at 300 $ elongation (module, abbreviated to "M 300", according to DIN (535O4)

3. The Shore A hardness (SE) according to DIN (53505)

4. The swelling of the molded body (q), that is, the volume increase in percent by volume after 28 days of storage i _n distilled setter.

Furthermore, the respective mixtures of the rheometer test (Test specimen preheated to 30/155 C) according to the pre-standard of October 1972 DIN 53529 and ^ ° the minimum torques (D.) In Nm and further the Mooney plasticity or viscosity (ML.4) (test specimen 30 ^ 150 C preheated) in Mooney units according to DIN 53523 and 53524 determined at 150 ° C with the Normal rotor (l) and a test duration of 4 minutes. The measured values were as follows:

ω σι

co ο

bo cn

cn

cn

Table I.

tensile strenght
MPa comparison
V1 1 . Module 300 7.5 2. Shore A hardness 1.4 3. Swelling
VoI # 43 if. Rheometer D ₄
._ min
Nm 1.71 5. Mooney MLU 0.29 6th 12th V1: without
V2: with Oil mixtures
V2 1 1, 0 3.8 76 6.72 1.76 101 5 silica
Silica

co
ο

to
cn

Table I (continued)

Specimen tensile strenght
MPa a) b) 1 c) d) e) f) B) H) i ) J) 3 1. Module 300 7.9 8th, 2 8.5 8.4 7.5 9.2 8.0 8.2 8th, 6th 8th, 0 2. Shore A hardness 3.1 3, 2.9 3.7 3.4 4.1 3.7 3.3 5, 8th 4, 3 · Swelling
VoI $> 72 71 47 67 66 75 72 72 75 68 72 47 4th Rheometer D.
Nm 1.52 1, 85 2.53 1.74 1.80 1.40 1.44 2.69 2, 10 2, 77 5. Mooney ML4 0.86 0, 0.80 0.71 0.79 0.93 0.75 1.25 1, 48 0, 6th 38 40 48 45 44 86 42 60 51

330537

As is apparent from Table I, by the addition of silica to thermoplastic rubber, the measured values for the modulus 3OOjdie Shore A hardness and the tensile strength increased considerably (sample bodies V1 and V2) _f, and thus the utility value can be increased articles produced in this manner.
At the same time it must be stated that the

Measured values for the swelling, rheometer D, and

min

Mooney-Viskos! Did MLjA with the silica-containing one Rise test specimen V2. This is to be assessed as disadvantageous.

The measured values obtained on specimens containing SiIan can be found, but show how, while maintaining the improvement achieved by the addition of silica, e.g. in the case of Shore A hardness and module 300, the significant deterioration that occurred at the same time in particular e.g. the swelling value through the addition reversed from organosilanes to the mixture

can be. 20th

_ 26. 1 sample group B

In a basic mixture of 50 parts by weight of two thermoplastic rubbers based on styrene-butadiene-styrene copolymers, Cariflex ^ TR-4130, (Shell) and Solpren ^{VB /} 475 (Phillips Petroleum), 10 parts by weight of polystyrene, 15 parts by weight of plasticizer oil (Cattinex 9Λ5), 0.3 parts by weight of di-lauryl thiodipropionate (DLTDP) as an antioxidant and 0.3 parts by weight of a UV stabilizer (Tinuvin 326) are from 0.1 to 15 parts by weight of an organosilane, based on 100 parts by weight of the thermoplastic rubber, incorporated. Bis- (triethoxysilylpropyl) -tetrasulfane is used as the organosilane.

- ρ- The mixtures each contain 50 parts by weight as filler the precipitated silica already mentioned in example group A.

The comparison mixture does not contain any organosilane. on In addition to the test methods described above, the test specimens produced using the method described above are also tested for elongation at break, which is given in ° fo (DIN 5350 ^, point 2.3)

H H

Φ H H Φ .Q

O VD tv T- α Ω 00 CO ^ t • Η Φ T- ε • Ρ VO O Φ ο VO ON ε ε ΡΛ »Λ »Λ O * Λ O £ ·> φ t- 00 O S. O VO νο CV ΐΛ • ο • κ η O CV O »Π Jt CO t- ^ " Os ■ * Jt O VO Ο \ VO vo O t » »Π O VO N T- 00 * * ■ " ·> O O νο νο Os τ— £> - O VO ·· O ■ Ρ H CO A ■ Φ ic φ
■ Ρ Jt («Φ (H
WJ S. 5 ^Η S. K H φ φ I. 60 α ι φ Ö ^ R. φ ο. A. (4th pj $> O 0 H H 0 α φ Bru HO ο Φ> O *

- 28 -

1 It can be seen that the organosilane-containing test specimens show significantly higher elongation at break and the Shore A hardness increases in the desired manner.

5 Even with a content of 0.1 part by weight of organosilane there is a clear reduction in the barrel uptake of the test specimen compared to the comparison sample.

The use of organosilanes according to the invention therefore helps that which occurs through the incorporation of fillers into thermoplastic rubbers To alleviate disadvantages such as increased water intake or to eliminate, and at the same time even leads to an improvement of application-technically significant Properties of the end products made from the thermoplastic rubbers.

Claims (1)

10 claims . ■ '"* 'Elastic molding compound containing or consisting of a (m) thermoplastic rubber or a (em) mixture of such rubbers, optionally in a mixture with a thermoplastic and / or a synthetic resin, furthermore at least one (m) silicate filler in amounts of 1-300 Parts by weight, processing or Plasticizer oil in amounts of 0-100 parts by weight, and at least one stabilizer from the group of aging, fatigue, oxidation, ozone and light protection agents in customary amounts, characterized in that the molding compound has at least one organosilicon compound which has at least one alkoxysilyl group, in amounts of 0.1-25 parts by weight, all parts by weight being based on 100 parts by weight of thermoplastic rubber, or that the molding composition contains the organosilicon compound or organosilicon compounds mentioned as a premix with the silicate filler, or that the molding compound contains the said organosilicon compound or the said organosilicon compounds in a form chemically bonded to the silicate filler in a uniform distribution. 2. Elastic molding composition according to claim 1, characterized in that it is at least one organosilane of the formulas as organosilicon compounds X-CH- _Λ -SiR ¹ (OR) _o , ρ m 2m + 1 -pn ^v '3-n. ' in which X is chlorine or bromine, ρ = 1 or 2, m = 1 to 5 »R is a C ₁ - to C_ -alkyl group, a C - to C / - cycloalkyl group or the phenyl group, R is a C - to C _e -Alkyl group, a C_ - to C, - cycloalkyl group, the methoxyethyl group, the ethoxyethyl group, phenyl group or the benzyl group and η = 0.1 or 2, including a hydrolyzate and / or a condensate, II [ ^R n ( ^R0 ) ₃ -n ^Si - ( ^Alk ) _q ( ^A -) ris _x or III R ¹ ( ^R °) Si-AIk-SH ₅ in which Ar is an arylene radical with 6 to 12 atoms, r = 0 or 1, R is a Cj to C "alkyl group, the phenyl group, R a C- to C _- * alkyl group, the methoxyethyl group, the ethoxyethyl group, Phenyl group or the benzyl group j, n = 0, 1 or 2, Alk is a divalent, straight or branched hydrocarbon radical having 1 to 6 carbon atoms and χ a number from 2.0 to 8.0 including theirs Hydrolysates and / or their KondeasateqeO or 1 and as silicate fillers at least one filler taken from an aqueous medium by precipitation, which consists essentially of silica with specific Surfaces, measured according to DIN 66132, between 30 and 250 m / g, or that they are a mixture from or a chemical reaction product with at least one of the mentioned silica fillers or contains soot. 3. Elastic molding compound according to claim 1, characterized in that it contains at least one organosilane of the formula 10 as the organosilicon compound IV ASiR in which R is a C- to C_-alkyl group, R is a C ₁ - to C ^ -alkyl group, the methoxyethyl, the ethoxyethyl group, the phenyl or the Ben- zyl group, η m O; 1 or 2, A is an azido, thiocyanato, amino or epoxyalkyl group, the alkyl radical being a straight or branched hydrocarbon radical having 1 to 6 carbon atoms, or a vinyl group or an aralkyl radical. 4. A method for producing and deforming the elastic molding compound according to claims 1 to 3, characterized in that first in a high-speed internal mixer in a time of 2 to 30 minutes at a number of revolutions of 20 to 120 per minute and an initial temperature of 90 to 110 C mixes the thermoplastic rubber with the silicate filler (in one or more identical positions one after the other) and the organosilane and the mass on mixing rollers at an initial temperature (of the rollers) of 35 ο 90 to 110 C within a period of 1 to 10 Minutes into a uniform rolled head, meanwhile, cut or cut through the ¥ alz skin three to five times (with a knife) (and overturned), and that finally, if necessary, after cooling, the roller head with a Thickness of 2 to 20 mm taken from the mixing roller device, optionally into granules or the same common shaped pieces are crushed and these at temperatures between 60 and 300 C with Is processed using conventional devices to moldings. 5. A method for producing and shaping the elastic molding compound according to claims 1 to 4, characterized in that first in a high-speed internal mixer in a time of 2 to 30 minutes with a number of revolutions of 20 to 120 per minute and an initial temperature of 90 to 110 C _s mixing the thermoplastic rubber with the synthetic resin to this mixture the silicate filler, processing or softening oils and the organosilane are then added to aging and UV protection and further processes the resulting mass on mixing rolls. 6. Use of the elastic molding compound according to the Claims 1 to 5 for the production of shoe soles, Sole plates, heels, heel plates or other moldings as well as extruded threads, Cords, tapes, profiles, hoses or Plates.